This invention relates to oxidation colorants containing special combinations of primary intermediates for coloring keratin fibers.
By virtue of their intensive colors and good fastness properties, so-called oxidation colorants play a prominent role in the coloring of keratin fibers, particularly human hair. Oxidation colorants contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates in the presence of oxidizing agents or atmospheric oxygen.
Good oxidation dye precursors are expected to satisfy above all the following requirements: they must form the required color tones with sufficient intensity and fastness during the oxidative coupling reaction. In addition, they must be readily absorbed onto the fibers with no significant differencesxe2x80x94particularly in the case of human hairxe2x80x94between damaged and freshly regrown hair (levelling behavior). They must be resistant to light, heat and the effect of chemical reducing agents, for example permanent wave lotions. Finally, if they are used to color hair, they should not overly stain the scalp and, above all, should be toxicologically and dermatologically safe.
The primary intermediates normally used are primary aromatic amines containing another free or substituted hydroxy or amino group in the para position or the ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.
Special representatives are, for example, p-tolulenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylene-diamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone and 4-amino-3-methylphenol, 2-hydroxy4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminohydroxypyrimidine.
The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and pyridine derivatives. Particularly suitable secondary intermediates are xcex1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 2-chloro6-methyl-3-aminophenol, 2-methyl resorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.
With regard to other dye components, reference is expressly made to the Colipa-Liste published by the Industrieverband Kxc3x6rperpflege und Waschmittel, Frankfurt.
By combination with various secondary intermediates, a certain primary intermediate can form a broad range of color tones. Nevertheless, it is often not possible to obtain the large range of natural color tones with a single primary intermediate. In practice, therefore, a combination of various primary intermediates and secondary intermediates has to be used to obtain a single natural-looking color. Accordingly, there is a constant need for new improved secondary intermediate/primary intermediate combinations. This applies in particular to the red range where conventional dyes are often not entirely satisfactory in their fastness to rubbing, their level-dyeing capacity and their resistance to cold waving and washing.
Accordingly, the problem addressed by the present invention was to provide new primary intermediate combinations and suitable secondary intermediates which would satisfy the requirements oxidation dye precursors are expected to meet to a particular degree.
It has now surprisingly been found that special combinations of known primary intermediates, especially in combination with certain, similarly known secondary intermediates, lead to intensive colors, above all in the red and orange range, which are distinguished inter alia by particularly high fastness to light, washing and rubbing and by surprisingly good levelling behavior.
Accordingly, the present invention relates to oxidation colorants for coloring keratin fibers containing primary intermediates and secondary intermediates in a water-containing carrier, characterized in that at least one pyrimidine derivative containing 2-4 amino substituents and 0-2 hydroxy substituents on the pyrimidine ring in combination with 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene and/or 2-(2xe2x80x2-hydroxyethylamino)-5-aminotoluene is present as the primary intermediate.
In the context of the invention, keratin fibers are understood to include pelts, wool, feathers and, in particular, human hair. Although the oxidation colorants according to the invention are particularly suitable for coloring keratin fibers, there are no basic obstacles to their use in other fields, particularly in color photography.
Pyrimidine derivatives containing 2 to 4 amino substituents and 0 to 2 hydroxy substituents on the pyrimidine ring are used as primary intermediate in the oxidation colorants according to the invention. These pyrimidine derivatives, for example 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-tri-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine and 2,4-dihydroxy-5,6-diaminopyrimidine, are compounds familiar to the expert. DE-OS 23 59 399 and the book by Kh. Schrader entitled xe2x80x9cGrundlagen und Rezepturen der Kosmetikaxe2x80x9d, Dr. Afred Hxc3xcthig Verlag, Heidelberg, 2nd Edition, are cited as representative of the numerous publications in which these compounds are disclosed.
More particularly, specific reference is made to DE-OS 23 59 399 where it discloses the production of the compounds.
Particularly preferred pyrimidine derivatives, which may be used both on their own and in combination with one another, are 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.
So far as the component 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene is concerned, reference is made in particular to the disclosure of DE-A1 39 17 304 which describes this component under the name of 2-(2,5-diamino-phenyl)-ethanol and also discloses its use in hair colorants.
So far as the component 2-(2xe2x80x2-hydroxyethylamino)-5-aminotoluene is concerned, reference is made in particular to the disclosure of DE-C1 43 01 663.
However, there is nothing in any of these documents which points to the combinations according to the invention.
The primary and secondary intermediates present in the formulations according to the invention may be used both as free bases and in the form of their inorganic or organic salts, for example hydrochlorides, sulfates and hydrobromides.
In addition, it has been found that colors exhibiting particularly favorable properties are obtained where the formulations according to the invention contain m-aminophenols corresponding to formula (I): 
in which R1 is hydrogen, a methyl group, an ethyl group or a hydroxyalkyl group containing 2 or 3 carbon atoms and R2 and R3 independently of one another are hydrogen or chlorine, as secondary intermediates.
Particularly suitable secondary intermediates corresponding to formula (I) are 2-methyl-5-aminophenol, 2-methyl-5-xcex2-hydroxyethylaminophenol and 3-amino-2-chloro-6-methylphenol.
Formulations which contain certain other secondary intermediates in addition to those corresponding to formula (I) are also distinguished by unexpectedly good coloring results. These other secondary intermediates are preferably selected from
resorcinol and resorcinol derivatives,
naphthalene derivatives containing at least one OH group and
pyridine derivatives containing at least one C1-4 alkyl group and at least one hydroxy group.
Particularly suitable other secondary intermediates are resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 4-chlororesorcinol, 1,5-, 1,7- and 2,7-dihydroxynaphthalene and 2,6-dihydroxy-3,4-dimethylpyridine.
The hair colorants according to the invention contain both the primary intermediates and the secondary intermediates in a quantity of preferably 0.01 to 20% by weight and, more preferably, 0.5 to 5% by weight, based on the oxidation colorant as a whole. The primary intermediates and secondary intermediates are generally used in substantially equimolar quantities. Although the equimolar amounts of primary and secondary intermediates have proven expedient, a certain excess of individual oxidation dye precursors is not a disadvantage, so that the primary intermediates and secondary intermediates may be present in a molar ratio of 1:0.5 to 1:2.
In addition to the primary intermediate or secondary intermediate/primary intermediate combinations according to the invention, the hair colorants may optionally contain other primary intermediates and/or secondary intermediates to obtain special color tones. Suitable compounds were mentioned in the acknowledgement of the prior art.
In one preferred embodiment, the hair colorants according to the invention contain typical substantive dyes in addition to the oxidation dye precursors in quantities of 0.01 to 20% by weight, based on the oxidation hair colorant as a whole, for further modifying the color tones. The typical substantive dyes in question may be selected, for example, from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, or example the compounds known under the international names or trade names of HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitroblau, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, picramic acid and Rodol 9 R.
The oxidation dye precursors and the substantive dyes optionally present do not have to be single compounds. Instead, the hair colorants according to the inventionxe2x80x94due to the processes used for producing the individual dyesxe2x80x94may contain small quantities of other components providing they do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons.
To produce the colorants according to the invention, the oxidation dye precursors are incorporated in a suitable water-containing carrier. For coloring hair, such carriers are, for example, cremes, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair.
The hair colorants according to the invention are adjusted to a pH value of preferably 7 to 11 and, more preferably, 9 to 10.
The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants can be particularly useful,
Suitable anionic surfactants for the hair colorants according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ether, amide and hydroxyl groups andxe2x80x94generallyxe2x80x94ester groups may also be present in the molecule. The following are examples of suitable anionic surfactantsxe2x80x94in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group:
linear and branched fatty acids containing 8 to 22 carbon atoms (soaps),
ether carboxylic acids corresponding to the formula Rxe2x80x94Oxe2x80x94(CH2xe2x80x94CH2O)xxe2x80x94CH2xe2x80x94COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x=0 or 1 to 16,
acyl sarcosides containing 10 to 18 carbon atoms in the acyl group,
acyl taurides containing 10 to 18 carbon atoms in the acyl group,
acyl isethionates containing 10 to 18 carbon atoms in the acyl group,
sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
linear alkane sulfonates containing 12 to 18 carbon atoms,
linear xcex1-olefin sulfonates containing 12 to 18 carbon atoms,
xcex1-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula Rxe2x80x94O(CH2xe2x80x94CH2O)xxe2x80x94OSO3H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x=0 or 1 to 12,
mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C8-22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one xe2x80x94COO(xe2x88x92)or xe2x80x94SO3(xe2x88x92) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine.
Ampholytic surfactants are surface-active compounds which, in addition to a C8-18alkyl or acyl group, contain at least one free amino group and at least one xe2x80x94COOH or xe2x80x94SO3H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine.
Nonionic surfactants contain, for example, a polyol group, a poly-alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are
products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide to linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols containing 8 to 15 carbon atoms in the alkyl group,
C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide to glycerol,
C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof,
products of the addition of 5 to 60 moles of ethylene oxide to castor oil and hydrogenated castor oil,
products of the addition of ethylene oxide to sorbitan fatty acid esters,
products of the addition of ethylene oxide to fatty acid alkanolamides.
Examples of cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates.
Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil(copyright)-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80).
Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid(copyright)S 18, are distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability.
Quaternary ester compounds, so-called xe2x80x9cesterquatsxe2x80x9d, such as the dialkyl ammonium methosulfates and methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex(copyright), are also readily biodegradable.
One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat(copyright)100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).
The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained.
The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a xe2x80x9cnormalxe2x80x9d homolog distribution and products with a narrow homolog distribution. Products with a xe2x80x9cnormalxe2x80x9d homolog distribution are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be of advantage.
Other active substances, auxiliaries and additives are, for example,
nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes,
cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quaternized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers,
thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, carob bean flour, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol,
structurants, such as glucose, maleic acid and lactic acid,
hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils,
protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates,
perfume oils, dimethyl isosorbide and cyclodextrins,
solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
dyes for coloring the formulations,
antidandruff agents, such as Piroctone Olamine and Zinc Omadine,
alkalizing agents such as, for example, ammonia, monoethanolamine, 2-amino-2-methylpropanol and 2-amino-2-methylpropane-1,3-diol,
other substances for adjusting the pH value,
active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins,
cholesterol,
UV absorbers,
consistency promoters, such as sugar esters, polyol esters or polyol alkyl ethers,
fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
fatty acid alkanolamides,
complexing agents, such as EDTA, NTA and phosphonic acids,
swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
opacifiers, such as latex,
pearlescers, such as ethylene glycol mono- and distearate,
propellents, such as propane/butane mixtures, N2O, dimethyl ether, CO2 and air and
antioxidants.
To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole.
Basically, the color may be oxidatively developed with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, particularly when human hair is to be not only colored, but also lightened. Particularly suitable oxidizing agents are hydrogen peroxide or addition products thereof with urea, melamine or sodium borate. Oxidation may also be carried out with enzymes. In this case, the enzymes may be used both to produce oxidizing per compounds and to enhance the effect of an oxidizing agent present in small quantities. One example of an enzymatic process is the procedure whereby the effect of small quantities (for example 1% and less, based on the formulation as a whole) of hydrogen peroxide is enhanced by peroxidases.
The preparation of the oxidizing agent is best mixed with the preparation of the oxidation dye precursors immediately before coloring of the hair. The ready-to-use hair coloring preparation formed should preferably have a pH value of 6 to 10. In a particularly preferred embodiment, the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 40xc2x0 C. After a contact time of about 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant content, for example a coloring shampoo, has been used.